CN102443113B - Preparation method of adjustable temperature-responsive star hybrid material using POSS as nucleus - Google Patents
Preparation method of adjustable temperature-responsive star hybrid material using POSS as nucleus Download PDFInfo
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- CN102443113B CN102443113B CN 201110338703 CN201110338703A CN102443113B CN 102443113 B CN102443113 B CN 102443113B CN 201110338703 CN201110338703 CN 201110338703 CN 201110338703 A CN201110338703 A CN 201110338703A CN 102443113 B CN102443113 B CN 102443113B
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Abstract
The invention belongs to the fields of high-molecular material and biomedical engineering, and specifically relates to a preparation method of an adjustable temperature-responsive star hybrid material using POSS (Polyhedral Oligomeric Silsesquioxane) as a nucleus. The method comprises steps of: using octa(gamma-chloropropyl) as an initiator, carrying out atom transfer radical polymerization on 2-methyl-2-acrylic acid-2-(2-methoxy ethoxy) ethyl ester and polyethylene glycol methyl ether metacrylic acid ester monomer to generate a temperature-sensitive hybrid material, a lower critical solution temperature (LCST) of which can be adjusted through proportion of the two monomers. The star hybrid material using POSS as the nucleus of the invention has adjustable temperature-responsiveness and can carry out self-assembly in water into stable nano micelle; therefore, the hybrid material can be widely applied to fields of drug controlled release carrier, biological intelligent switch, biosensor and biological nano device, etc. The synthetic method of the invention is simple and practical, uses raw materials from industrialized production and has good popularization and application value.
Description
Technical field
The invention belongs to macromolecular material and biomedical engineering field, be specifically related to a kind of POSS and be the preparation method of the adjustable temps susceptibility star hybrid material of nuclear.
Background technology
Multiaspect oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is a kind of oligosiloxane of nanoscale cage structure, and its general structure is (RSiO
1.5) n, n=6,8,12 etc., R is organo-functional group.Itself has core-shell structure POSS, and shell and polymer that the R group consists of have good consistency, can significantly improve by the method for physical blending the resistance toheat of macromolecular material.R group with reactive behavior then can trigger monomer polymerization, realize the connection of inorganic/organic materials on molecular level.Wang Wen equality (Wang Wenping, Fei Ming, Wang Peng, Cao Hengming is made known dawn, the polymer circular, 2010,7,83-86) method by atom transfer radical polymerization has prepared the POSS/ polymkeric substance of different topology structure and has compared its thermostability.(Zhao Chunbao, Jin Hong, the Yang Xujie such as Zhao Chunbao, New Chemical Materials, 2011,39(3), 47-57) at the basis of eight (aminophenyl) silsesquioxane (OAPS) preparation ATRP initiator B OAPS, further cause the hybrid material to star structure of MMA monomer polymerization.The linear PMMA close with molecular weight compares, and second-order transition temperature and the heat decomposition temperature of hybrid material all are significantly increased.
The environmental sensitivity polymkeric substance is that a class can be made response to the variation of the external environments such as pH, temperature, UV-light, and produces the macromolecular material of respective physical structure and chemical property even sudden change.This base polymer is owing to its unique performance gets more and more people's extensive concerning.The multipolymer of 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester (Di (ethylene glycol) methyl ether methacrylate) and methoxypolyethylene glycol methacrylic ester (Poly (ethylene glycol) methyl ether methacrylate) is common temperature-responsive polymkeric substance, and its lowest critical solution temperature (LCST) can be regulated by changing two kinds of monomers ratio in multipolymer.(Yuan, the W.Z. such as Yuan Weizhong; Zhang, J.C.; Wei, J.R.; Yuan, H.; Ren, J.; J Polym Sci Part A:Polym Chem, 2011,49,4071-4080.) having prepared 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol alkylmethacrylate polymer is the dendroid star-like macromolecules of Y type side arm.
Utilize the reactable of the upper R functional group of POSS, method in conjunction with ATRP, introduce the multipolymer of 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester, methoxypolyethylene glycol methacrylic ester on the POSS nuclear, fast synthetic adjustable temps responsiveness eight arm star POSS/ organic Hybrid Materials, this will have widespread use in fields such as biomedicines.
Summary of the invention
The object of the present invention is to provide a kind of POSS to be the preparation method of the adjustable temps susceptibility eight arm star hybrid materials of nuclear.
The objective of the invention is the temperature-responsive polymkeric substance is incorporated on the POSS nuclear as side arm, make the eight arm star polymers that obtain have good temperature sensitivity, and its LCST can regulate by the ratio of polymkeric substance different components.The present invention is take eight chloropropyl POSS as initiator, commercial 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester, methoxypolyethylene glycol methacrylic ester are monomer, adopt the method for atom transfer radical polymerization, prepare the POSS of a series of different 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylic ester copolymerization ratio side arm and be the adjustable temps responsiveness star hybrid material of nuclear.
The POSS that the present invention proposes is the preparation method of the adjustable temps responsiveness star hybrid material of nuclear, and concrete steps are as follows:
Eight chloropropyl POSS are dissolved in solvent, and according to chloro end-blocking POSS initiator several 10～100 times amount of chloride atomic molar add monomer 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylic ester.Under catalyst action, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 20～100 ℃, and the reaction times is 1～48 hour, remove catalyzer after, and through the dialysis, lyophilize, namely obtain required product.
Among the present invention, described solvent is dimethyl sulfoxide (DMSO), chloroform, DMF, N, one or more in N-diethylformamide or the N,N-dimethylacetamide.
Among the present invention, described catalyzer is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or the cuprous bromide/hexamethyl Triethylenetetramine (TETA).
Among the present invention, the mol ratio of described 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylate monomer is 50:1-4:1.
The invention has the advantages that: raw material sources are extensive, eight used chloropropyl POSS, 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) but equal suitability for industrialized production such as ethyl ester and methoxypolyethylene glycol methacrylate monomer, solvent, catalyzer, synthetic method is simple.Synthetic eight arm star hybrid materials take POSS as nuclear have temperature sensitivity, and its LCST can regulate by the ratio of polymkeric substance different components on the side arm.Because the polymkeric substance side arm has wetting ability below LCST, POSS nuclear itself has hydrophobicity, and this hybrid material can self-assembly be stable nanometer micelle in water.The micella particle diameter can be regulated by the length that changes 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylic ester random copolymers.Gained hybrid material adjustable temps responsiveness, thereby have widely in fields such as medicine control release vehicle, nanometer microreactor, biological intelligence switch, biosensors and to use.
Description of drawings
Fig. 1 is that the POSS of embodiment 1 preparation is the structural representation of the adjustable temps responsiveness star hybrid material of nuclear.
Embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
This POSS measures with Fourier transform infrared spectrometer (FTIR) and magnetic nuclear resonance analyzer (NMR) for the molecular structure of the adjustable temps responsiveness star hybrid material of nuclear.Molecular weight is measured by gel permeation chromatography (GPC).Self-assembly gained micella is measured with transmission electron microscope (TEM) and atomic force microscope (AFM).The micella particle diameter is measured with dynamic laser light scattering apparatus (DLS).
Embodiment 1
Take by weighing 80mg eight chloropropyl POSS; be dissolved in dimethyl sulfoxide (DMSO); add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 4g, methoxypolyethylene glycol methacrylic ester 0.8g; add again catalyzer cuprous bromide (60 milligrams)/pentamethyl-diethylenetriamine (150 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 30 ℃ of lower reactions 36 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Representative structure formula take POSS as the adjustable temps responsiveness star hybrid material of nuclear as shown in Figure 1.
Embodiment 2
Take by weighing 80mg eight chloropropyl POSS; be dissolved in N; dinethylformamide; add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 4.3g, methoxypolyethylene glycol methacrylic ester 0.6g; add again catalyzer cuprous chloride (90 milligrams)/pentamethyl-diethylenetriamine (250 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 70 ℃ of lower reactions 6 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Embodiment 3
Take by weighing 60mg eight chloropropyl POSS; be dissolved in chloroform; add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 3.8g, methoxypolyethylene glycol methacrylic ester 1.2g; add again catalyzer cuprous chloride (90 milligrams)/dipyridyl (150 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 50 ℃ of lower reactions 15 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Embodiment 4
Take by weighing 60mg eight chloropropyl POSS; be dissolved in N; dinethylformamide; add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 4g, methoxypolyethylene glycol methacrylic ester 0.6g; add again catalyzer cuprous chloride (90 milligrams)/dipyridyl (200 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 70 ℃ of lower reactions 36 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Embodiment 5
Take by weighing 60mg eight chloropropyl POSS; be dissolved in dimethyl sulfoxide (DMSO); add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 4.2g, methoxypolyethylene glycol methacrylic ester 0.8g; add again catalyzer cuprous bromide (50 milligrams)/pentamethyl-diethylenetriamine (100 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 50 ℃ of lower reactions 6 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Embodiment 6
Take by weighing 70mg eight chloropropyl POSS; be dissolved in chloroform; add again 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester 4.5g, methoxypolyethylene glycol methacrylic ester 1.0g; add again catalyzer cuprous chloride (90 milligrams)/pentamethyl-diethylenetriamine (200 milligrams); through vacuumizing-inflated with nitrogen process 3 times, and under nitrogen protection in 25 ℃ of lower reactions 36 hours.The dialysis of product deionized water, lyophilize gets POSS and is the adjustable temps susceptibility star hybrid material of nuclear.
Claims (3)
1. a POSS is the preparation method of the adjustable temps responsiveness star hybrid material of nuclear, it is characterized in that concrete steps are as follows:
Initiator eight chloropropyl POSS are dissolved in solvent, and according to chloro end-blocking POSS initiator several 10～100 times amount of chloride atomic molar add monomer 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylic ester; Under catalyst action, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 20～100 ℃, and the reaction times is 1～48 hour, remove catalyzer after, and through the dialysis, lyophilize, namely obtain required product; Wherein: the mol ratio of 2-methyl-2-vinylformic acid-2-(2-methoxy ethoxy) ethyl ester and methoxypolyethylene glycol methacrylate monomer is 50:1-4:1.
2. POSS according to claim 1 is the preparation method of the adjustable temps responsiveness star hybrid material of nuclear, it is characterized in that described solvent is dimethyl sulfoxide (DMSO), chloroform, N, dinethylformamide, N, one or more in N-diethylformamide or the N,N-dimethylacetamide.
3. POSS according to claim 1 is characterized in that for the preparation method of the adjustable temps responsiveness star hybrid material of nuclear described catalyzer is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or the cuprous bromide/hexamethyl Triethylenetetramine (TETA).
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| CN103694426B (en) * | 2013-11-25 | 2015-10-21 | 同济大学 | A kind of preparation method of the multiple response type polymkeric substance containing base pair |
| CN104045779A (en) * | 2014-06-25 | 2014-09-17 | 南通茂林医用材料有限公司 | Preparation method of temperature/CO2 dual response star-shaped hybrid material taking POSS (Polyhedral Oligomeric Silsesquioxane) as kernel |
| CN105669924B (en) * | 2016-04-21 | 2018-08-21 | 厦门大学 | The organic inorganic hybridization block copolymer and its synthetic method of the structure containing POSS |
| CN107868192B (en) * | 2016-09-27 | 2020-07-24 | 中国石油化工股份有限公司 | Methoxy polyethylene glycol-polymethacrylate block copolymer and preparation method and application thereof |
| CN106832339B (en) * | 2017-02-24 | 2018-10-26 | 中南大学 | A kind of organic-inorganic hybrid nanometer particle and preparation method thereof based on hexahedron oligomeric silsesquioxane and ferrocene |
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